When I recalculate Bone Roll in Edit Mode the recalculation doesn't transfer over to pose mode
Its because you use IKs. They are only calculated in Pose Mode. If you are using IKs its really important that your Bones that are affected are not in a straight line, else the algorithm will not know in which direction to bend. Also in the IK settings there is a Pole Angle with which you can experiment after you created that bend. To create that bend I recommend to move the knee connection almost to the skin, that will help later with deformation